1. Field of Invention
The present invention relates to a polymer composite and the producing method thereof, and more particularly to a method for modifying soil to produce composite elastomer.
2. Description of Related Arts
It is common that in the process for producing plastic, rubber, paint, or cables, fillers are generally added into the raw materials of the compound to reduce the costs and improve the physical properties of the raw materials. The key point is to find out the relations between the fillers and the organic compounds, so as to maximize the physical properties or to minimize the cost for producing the compounds. The soil is one of the cheapest fillers that can be found everywhere. At present, non-metallic mineral soil is one of the most common fillers for adding into the producing process, such as kaolin, attapulgite, bentonite, clay, and coal gangu. How to add the non-metallic mineral soil in the producing process without affecting or decreasing the physical properties of the materials is the focus of the research for the synthesizing process. There are some publications introducing the characteristics of modified non-metallic soil as followings.
1. Title: The Affection of Modified Calcined Kaolin on the EPDM's Function. Author: ShuZhan, Y E; YanHao, ZHOU; FuLin, CHEN. Institution: Materials and Energy College, GuangDong University of Technology. Journal: China Rubber Industry, 2006, 53(12).-723-726. Summary: A silane coupling agent is used for surface-modification of calcined kaolin, wherein the study of variety and amount of silane coupling agents on the calcined kaolin EPDM plasticity properties is conducted. The results show that silane coupling agent has a minor effect on the burn time and vulcanization time of the calcined kaolin substance EPDM plastic. The coupling agent, A17Z, has a more significant modifying effect and is able to enhance the tear strength of the EPDM vulcanization. The excessive amount of coupling agent A17Z is used, it will reduce the solvent-ability of EPDM vulcanizate.
2. Title: The surface modification of Sedimentary calcined kaolin in Yichang and Its Application. Author: WangChi, ZHANG [1,2]; Ming'an, HU [1]; JinFa, LI [2]; YanBo, CHEN [2]. Institution: (1) Graduate School of China University of Geosciences (2) Yichang Institute of Geology and Minerals Resources. Summary: sedimentary kaolin is the unique resource of kaolin in China. The study shows that Yichang sedimentary kaolin, used as the substance of high performance electric cable, can significantly improve the physical properties of the electric cable after the sedimentary kaolin is being pulverized, calcined, grinded, and surface modified by the silane coupling agent.
3. Title: The Producing of A surface-modified attapulgite reinforced rubber. Author YuanSun, WANG. Institution: unknown. Journal: China Rubber/Plastics Technology and Equipment. Summary: The method for improving the compatibility and filler effect of rubber through the organically surface modifying of attapulgite clay, wherein the yield strength, 300% elongation, and tear strength are significantly increased. Thus, the vulcanization time is shorter, sulfide cross-linking effect is enhanced. This product is able to widely use for the high strength rubbers.
4. Title: The Feasibility Study on the Modified Dolomite Attapulgite Appling into Rubber Filling. Author YeLing, JIN; YunHua, QIAN. Institution: Chemical Engineering Department, Huaiyin Institute of Technology. Journal: Journal of Nanjing University of Science and Technology (University of Science and Technology): 2005, 29(6).-720-723. Summary: The study disclosed the natural composite filling feasibility of modified Dolomite-Attapulgite in rubber, wherein the modified Dolomite-Attapulgite is mechanically tested and microstructure observed. The results show that the filling of plastic substance in the dolomite-attapulgite modified by the stearic acid is significantly increased, which can reach 110 g/100 g plastic substance, so as to have excellent compatibility, shorten the mixing time, enhance the elongation ability, smoothen and flatten the surface of the plastic substance, and enhance the glossness. Compared the modified dolomite-attapulgite with the precipitated calcium carbonate, dolomite-attapulgite can significantly improve the tensile strength of filled rubber-like, 300% elongation, elongation at break and adhesion strength, which are increased 57.8%, 100%, 5.5%, 16% respectively compared with light-filled plastic Ca sample.
5. Title: The Surface-modified Coal calcined kaolin and Its Application in Polymer Products. Author BaoZhi, LI[1]; WenLi, WANG[2]. Institution: (1) Rechi Surface Modifiers Factory in Baotou, Inner Mongolia Province (2) Technical Information of China Building Materials. Institution Non-Metallic Mines. 2005, 28(B09).-49-51. Summary: the article mainly introduced the nature of the coal-bearing series of kaolin, wherein it disclosed the application result after calcination the surface modification mechanism, methods, equipment selection, as well as the calcined soil in plastic, rubber, paint, etc.
6. Title: The Production of Bentonite/PAA superabsorbent material and Its Modification. Author: YueLin, W E I; JiHuai, W U; YunFang, HUANG. Institution: Huaqiao University. Journal: Journal of Huqiao University (Natural Science) 2005, 26(4).-365-368. Summary: High-temperature rapid solution polymerization method. Synthesis of bentonite/polyacrylate superabsorbent composite, wherein the study disclosed the variety affects during the preparation of composite material, such as the effect of cross-linking agent amount and ultra-fine powder amount on water absorption. The article also mentioned about modifying the surface of cross-linking composite materials. The results showed that the modified composite materials can help to improve water absorption and water absorption rate.
7. Title: Surface-modified Kaolin and Its Application in Rubber Cable. Author: XianZhong, CHENG[1]; Can, JIN[1]; XinHai, LIU[2]. Institution: [1] Yichang Institute of Geology and Mineral Resources [2] Zhengzhou Institute of Multipurpose Utilization of Mineral Resources. Journal: China Powder Industry. 2005(4).-34-37. Summary: The coal-bearing series of kaolin is China's unique kaolin resources. The study showed that the coal-bearing series of kaolin, through pulverization, Calcination, grind, and surface modification by the silane coupling agent, can be used as high physical properties of electric cable material, wherein the filling ability is significantly improved.
8. Title: The Surface-modified Attapulgite and Its Application in Boots Facial Plastic. Author: YunHua, QIAN; YeLing, J I N. Institution: Chemical Engineering Department, Huaiyin Institute of Technology. Journal: Non-Metallic Mines. 2005, 28(1).-17-18, 43. Summary: The Dolomite-Attapulgite is modified via the stearic acid, wherein the best condition for modifying is to use 2% stearic acid, at a modifying temperature of 80° C., and modifying time of 30 minutes, so that the activation index of the modified dolomite-attapulgite is about 0.95. The modified dolomite-attapulgite in the surface of the rubber made rain boot shows that the modified dolomite-attapulgite is able to completely replacing the light calcium.
9. Title: The Preliminary Study on The Surface modification of Nano-kaolin. Author: ZhuoQin, L I U; ZhenBang, P I; XiKe, TIAN. Institution: Faculty of Material Science & Chemistry Engineering, China University of Geosciences. Summary: Using variety of modifying agents for the surface modification of nano-kaolin, wherein the article discusses the mechanism of increasing the index via adding surfactant during the modification. Through the infrared analysis, the surface of the kaolin particle is linked with the coupling agent. The filling rubber test shows that the composite modified nano-kaolin has an excellent reinforcement effect.
10. Title: Study on the Surface modification of Sedimentary Kaolin and Its Application. Author: XinHai, L I U; YiBo, L I. Institution: Zhengzhou Institute of Multipurpose Utilization of Mineral Resources, Chinese Academy of Geological Sciences. Journal: China Powder Technology. 2005, 11(2).-6-8. Summary: The sedimentary kaolin is the unique natural source. The experiment shows that, used as the substance of good quality of electric cable, can significantly improve the physical properties of the electric cable after the sedimentary kaolin is pulverized, calcined, grinded, and surface modified by the silane coupling agent.
11. Title: Activation of Bentonite Modification and Its Application in Rubber. Author: LiYing, ZHAO; YinShan, JIANG. Institution: Jilin University. Journal: Multipurpose Utilization of Mineral Resources. 2004(2).-23-27. Summary: Use the method of heat treatment and mechanical-chemical modification of combining activated bentonite to prepare rubber reinforcing filler. The heat treatment can effectively reduce the volatile and integration of mineral water and activate structure to ensure and improve the effect of dry-mechanical-chemical surface modification, so that can obtain ideal index of using modifier less than 1%. The obtained bentonite by using this method can replace 30% of semi-reinforcing carbon black, and its physical properties of rubber products meet the national standard GB3778-94. If the high-abrasion furnace black is 100% replaced, the mechanical properties of the rubber can meet the GB318-98 Technical Requirements.
12. Title: Progress in Surface Modification of Kaolin. Author: XuHai, WANG; XuChen, L U. Institution: Energy and Materials Research Center of Institute of Process Engineering, Chinese Academy of Sciences. Journal: Industrial Minerals and Processing. 2004, 33(3).-1-3, 10. Summary: An overview of Research on Surface Modification of kaolin and modified kaolin applications, proposing future research directions.
13. China patent application, CN 200480036156. X. Title: preparation of Si rubber composition of kaolin. Applicant: Dow Corning Corporation. Address: Michigan, USA. Inventor: M•G•Proctor; R•M•Taylo. Date for entering national stage:
Jun. 5, 2006. Summary: Treatment of a kaolin containing silicone rubber composition, the composition essentially consists of the following components: an organic polysiloxane, processed kaolin; curing agent; and selected from one or more rheology modifiers, pigments, colorants, anti-adhesives, plasticizers, adhesion promoting agents, blowing agents, flame retardants and the desiccant in the optional additives. The composition is basically non-reinforcing filler. The final kaolin containing silicone rubber composition can be used, such as siloxane profile extrusion, wire and cable coatings, glass assembly and washers for structural purposes.
14. China patent application, CN 200410047914.X. Title: External fluorocarbon decorative coatings and manufacturing method. Applicant: China National Petroleum Corporation; China Petroleum Group, Engineering Technology Institute. Address: Shop Kang, Xicheng District, Beijing, No. 6, 6. Summary: The present invention relates to an external fluorocarbon decorative coatings and manufacturing method, which is heating, mixing, and grinding fluoride vinylidene fluoride water emulsion, hydroxyethyl cellulose, sodium polycarboxylate, alkyl phenol polyoxyethylene ether, polyether modified dimethyl polysiloxane, 2-amino-2-methyl-1-propanol, titanium dioxide, talc, kaolin, 2,2,4-trimethyl-1,3-pentanediol single-isobutyl ester, sodium polyacrylate, urethane-modified polyether, and fumed silica powder to form the coatings, which has the characteristic of environmental friendly of room temperature curing, wherein the coating membrane has excellent weather resistance, solvent resistance and stain resistance.
According to the above references, using a modifier to modify the non-metal mineral soil can produce a high compatibility with other polymer materials, shorten the mixing time, and significantly enhancing the yield strength, elongation rate, tear strength of the filling plastic material, rubber, paper, paints, or electric cable. However, there is no publications or reference of modifying normal soil (such as yellow soil, red soil, black soil, or white soil) to be used in inorganic filling material.
The elastomer products include elastomer sports flooring, elastomer wall and floor bricks, and synthetic leather etc. Most of the existing elastomer products are rubber or thermoplastic elastomer. The vulcanization process of rubber generates toxic gaseous, so as to harm the environment. The thermoplastic products have the physical properties of vulcanizate and the similar process performance of the soft plastic material. However, the thermal resistance thereof is not as good as rubber, so that when the temperature is increasing, the physical properties of the thermoplastic products are dramatically decreasing, so as to limit the applications thereof. Meanwhile, the compression deformation, recovery elasticity, and durability of the thermoplastic material are not as good as rubber. And its price is usually higher than rubber. The above elastomer has relied on chemical products. Even if using inorganic material as the filling or substance, the content of inorganic material is no more than 60%.
Recently, some references mentioned about using the acrylic ester as the raw material for making elastomer material. Below are some examples.
1. Title: The preparation of butyl acrylate copolymer elastomer and its properties. Author: SuLing Tong, YuanYou Li, XingHua Zhang; Institute: Materials and Energy College, GuangDong University of Technology; Journal: GuangDong Rubber 2004(7).-2-4. Summary: The article is about synthesizing butyl acrylate elastomer material, wherein the acrylonitrile and acrylic acid are added as comonomer for modifying. The product is tested for the hardness and the glass transition temperature. The results show that when the butyl acrylate is copolymerizing with acrylic acid and acrylonitrile, the hardness and glass transition temperature of the copolymer is increased corresponding to the increasing content of the acrylonitrile and acrylic acid, wherein the butyl acrylate has more significant effect on the hardness of the product.
2. Title: The method of preparation of porous PBA elastomer material of reverse concentrated emulsion. Author: HongJuan Chen, Chen Zhang, ZhongJie Du, HangQuan Li; Institute: Beijing University of Chemical Technology-Beijing Novel Polymer Materials and Processing Laboratory; Journal: China Synthetic Rubber Industry. Summary: Use the butyl acrylate as a monomer. Use the divinyl benzene as cross-linking agent. Use azobisisobutyronitrile as initiator agent, sorbitol anhydride monooleate as the emulsifier, and water as dispersed phase. Use the reversed-phase concentrated emulsion for preparing the bulb-hole structure of acrylic acid Ding Lu (PBA) elastomer materials and for studying the polymerization reaction temperature, amount of emulsifier, and the dispersed phase volume fraction of PBA elastomer material pore structure of foam, characterized by scanning electron microscopy of the foam pore structure. The results show that polymerization reaction temperature should be controlled to 50˜60° C. As the emulsifier mass fraction from 10% to 30%, the size of the pore of PBA elastomer gradually decreases, and the number of channels between the pores is increased. As the dispersed phase increasing volume fraction, PBA elastomer material of the pore diameter and channel diameter, speed incremental large porosity increased, the density are decreasing.
The above references disclosed acrylate copolymer elastomer and thermoplastic elastomer rubber have been solved the disadvantages of the existence products and provide a new material of application field. However, the acrylic ester copolymer elastomer practical application to industry and everyday life has not been reported. The uses of the acrylic emulsion copolymer and modified soil to form the composite elastomer materials are also not been reported.